EP0051678A4 - Process for producing spherical and porous vinyl resin particles. - Google Patents
Process for producing spherical and porous vinyl resin particles.Info
- Publication number
- EP0051678A4 EP0051678A4 EP19810901640 EP81901640A EP0051678A4 EP 0051678 A4 EP0051678 A4 EP 0051678A4 EP 19810901640 EP19810901640 EP 19810901640 EP 81901640 A EP81901640 A EP 81901640A EP 0051678 A4 EP0051678 A4 EP 0051678A4
- Authority
- EP
- European Patent Office
- Prior art keywords
- monomer
- polymer
- reaction
- surfactant
- dispersant
- Prior art date
- Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
- Granted
Links
- 239000002245 particle Substances 0.000 title claims abstract description 37
- 238000000034 method Methods 0.000 title claims abstract description 31
- 230000008569 process Effects 0.000 title claims abstract description 22
- 229920002554 vinyl polymer Polymers 0.000 title abstract description 13
- 239000011347 resin Substances 0.000 title description 10
- 229920005989 resin Polymers 0.000 title description 10
- 125000000391 vinyl group Chemical group [H]C([*])=C([H])[H] 0.000 title description 8
- 229920000642 polymer Polymers 0.000 claims abstract description 77
- 239000000178 monomer Substances 0.000 claims abstract description 76
- 239000004094 surface-active agent Substances 0.000 claims abstract description 49
- 238000006243 chemical reaction Methods 0.000 claims abstract description 47
- 239000002270 dispersing agent Substances 0.000 claims abstract description 23
- 238000013019 agitation Methods 0.000 claims abstract description 22
- 239000006185 dispersion Substances 0.000 claims abstract description 16
- 239000003054 catalyst Substances 0.000 claims abstract description 10
- 150000003254 radicals Chemical class 0.000 claims abstract description 5
- -1 nonylphenoxy Chemical group 0.000 claims description 60
- 238000006116 polymerization reaction Methods 0.000 claims description 48
- 229920003171 Poly (ethylene oxide) Polymers 0.000 claims description 41
- BZHJMEDXRYGGRV-UHFFFAOYSA-N Vinyl chloride Chemical group ClC=C BZHJMEDXRYGGRV-UHFFFAOYSA-N 0.000 claims description 19
- 239000012429 reaction media Substances 0.000 claims description 11
- NIXOWILDQLNWCW-UHFFFAOYSA-N 2-Propenoic acid Natural products OC(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-N 0.000 claims description 9
- SMZOUWXMTYCWNB-UHFFFAOYSA-N 2-(2-methoxy-5-methylphenyl)ethanamine Chemical compound COC1=CC=C(C)C=C1CCN SMZOUWXMTYCWNB-UHFFFAOYSA-N 0.000 claims description 8
- 229920002125 Sokalan® Polymers 0.000 claims description 5
- 230000000379 polymerizing effect Effects 0.000 claims description 5
- 238000004132 cross linking Methods 0.000 claims description 4
- 239000004584 polyacrylic acid Substances 0.000 claims description 4
- 125000003903 2-propenyl group Chemical group [H]C([*])([H])C([H])=C([H])[H] 0.000 claims description 2
- 229920006037 cross link polymer Polymers 0.000 claims description 2
- SNVLJLYUUXKWOJ-UHFFFAOYSA-N methylidenecarbene Chemical group C=[C] SNVLJLYUUXKWOJ-UHFFFAOYSA-N 0.000 claims description 2
- 239000012431 aqueous reaction media Substances 0.000 claims 1
- 238000003756 stirring Methods 0.000 abstract description 17
- 239000000375 suspending agent Substances 0.000 abstract description 15
- 239000000839 emulsion Substances 0.000 abstract description 14
- 150000001875 compounds Chemical class 0.000 abstract description 9
- 239000003513 alkali Substances 0.000 abstract description 5
- 239000012736 aqueous medium Substances 0.000 abstract description 4
- 150000001732 carboxylic acid derivatives Chemical class 0.000 abstract description 4
- HEMHJVSKTPXQMS-UHFFFAOYSA-M Sodium hydroxide Chemical compound [OH-].[Na+] HEMHJVSKTPXQMS-UHFFFAOYSA-M 0.000 description 36
- 239000000203 mixture Substances 0.000 description 20
- 206010001497 Agitation Diseases 0.000 description 18
- XLYOFNOQVPJJNP-UHFFFAOYSA-N water Substances O XLYOFNOQVPJJNP-UHFFFAOYSA-N 0.000 description 13
- 229920000570 polyether Polymers 0.000 description 11
- 239000000463 material Substances 0.000 description 10
- 150000002148 esters Chemical class 0.000 description 9
- 239000004721 Polyphenylene oxide Substances 0.000 description 8
- 239000002609 medium Substances 0.000 description 8
- 238000004945 emulsification Methods 0.000 description 7
- 239000004615 ingredient Substances 0.000 description 7
- KKEBXNMGHUCPEZ-UHFFFAOYSA-N 4-phenyl-1-(2-sulfanylethyl)imidazolidin-2-one Chemical compound N1C(=O)N(CCS)CC1C1=CC=CC=C1 KKEBXNMGHUCPEZ-UHFFFAOYSA-N 0.000 description 6
- PPBRXRYQALVLMV-UHFFFAOYSA-N Styrene Chemical compound C=CC1=CC=CC=C1 PPBRXRYQALVLMV-UHFFFAOYSA-N 0.000 description 6
- 239000002253 acid Substances 0.000 description 6
- 230000009471 action Effects 0.000 description 6
- RTZKZFJDLAIYFH-UHFFFAOYSA-N ether Substances CCOCC RTZKZFJDLAIYFH-UHFFFAOYSA-N 0.000 description 6
- 238000004519 manufacturing process Methods 0.000 description 6
- 239000000725 suspension Substances 0.000 description 6
- 239000011324 bead Substances 0.000 description 5
- 125000003178 carboxy group Chemical group [H]OC(*)=O 0.000 description 5
- 229910052739 hydrogen Inorganic materials 0.000 description 5
- 239000001257 hydrogen Substances 0.000 description 5
- XJRBAMWJDBPFIM-UHFFFAOYSA-N methyl vinyl ether Chemical compound COC=C XJRBAMWJDBPFIM-UHFFFAOYSA-N 0.000 description 5
- KAKZBPTYRLMSJV-UHFFFAOYSA-N Butadiene Chemical compound C=CC=C KAKZBPTYRLMSJV-UHFFFAOYSA-N 0.000 description 4
- LFQSCWFLJHTTHZ-UHFFFAOYSA-N Ethanol Natural products CCO LFQSCWFLJHTTHZ-UHFFFAOYSA-N 0.000 description 4
- 239000002202 Polyethylene glycol Substances 0.000 description 4
- CZMRCDWAGMRECN-UGDNZRGBSA-N Sucrose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO)O1 CZMRCDWAGMRECN-UGDNZRGBSA-N 0.000 description 4
- 229930006000 Sucrose Natural products 0.000 description 4
- QYKIQEUNHZKYBP-UHFFFAOYSA-N Vinyl ether Chemical compound C=COC=C QYKIQEUNHZKYBP-UHFFFAOYSA-N 0.000 description 4
- 150000007513 acids Chemical class 0.000 description 4
- 238000005054 agglomeration Methods 0.000 description 4
- 230000002776 aggregation Effects 0.000 description 4
- 230000015572 biosynthetic process Effects 0.000 description 4
- 239000003795 chemical substances by application Substances 0.000 description 4
- 238000009826 distribution Methods 0.000 description 4
- FJKIXWOMBXYWOQ-UHFFFAOYSA-N ethenoxyethane Chemical compound CCOC=C FJKIXWOMBXYWOQ-UHFFFAOYSA-N 0.000 description 4
- 229940052303 ethers for general anesthesia Drugs 0.000 description 4
- FPYJFEHAWHCUMM-UHFFFAOYSA-N maleic anhydride Chemical compound O=C1OC(=O)C=C1 FPYJFEHAWHCUMM-UHFFFAOYSA-N 0.000 description 4
- 125000006353 oxyethylene group Chemical group 0.000 description 4
- 239000004014 plasticizer Substances 0.000 description 4
- 229920001223 polyethylene glycol Polymers 0.000 description 4
- 239000004800 polyvinyl chloride Substances 0.000 description 4
- 239000000843 powder Substances 0.000 description 4
- 239000005720 sucrose Substances 0.000 description 4
- 238000012546 transfer Methods 0.000 description 4
- 229960000834 vinyl ether Drugs 0.000 description 4
- CMCBDXRRFKYBDG-UHFFFAOYSA-N 1-dodecoxydodecane Chemical compound CCCCCCCCCCCCOCCCCCCCCCCCC CMCBDXRRFKYBDG-UHFFFAOYSA-N 0.000 description 3
- CSHOPPGMNYULAD-UHFFFAOYSA-N 1-tridecoxytridecane Chemical compound CCCCCCCCCCCCCOCCCCCCCCCCCCC CSHOPPGMNYULAD-UHFFFAOYSA-N 0.000 description 3
- PEDCQBHIVMGVHV-UHFFFAOYSA-N Glycerine Chemical compound OCC(O)CO PEDCQBHIVMGVHV-UHFFFAOYSA-N 0.000 description 3
- WMFOQBRAJBCJND-UHFFFAOYSA-M Lithium hydroxide Chemical compound [Li+].[OH-] WMFOQBRAJBCJND-UHFFFAOYSA-M 0.000 description 3
- CERQOIWHTDAKMF-UHFFFAOYSA-N Methacrylic acid Chemical compound CC(=C)C(O)=O CERQOIWHTDAKMF-UHFFFAOYSA-N 0.000 description 3
- KWYUFKZDYYNOTN-UHFFFAOYSA-M Potassium hydroxide Chemical compound [OH-].[K+] KWYUFKZDYYNOTN-UHFFFAOYSA-M 0.000 description 3
- 150000008064 anhydrides Chemical class 0.000 description 3
- 230000008901 benefit Effects 0.000 description 3
- 229920001400 block copolymer Polymers 0.000 description 3
- 125000000484 butyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 3
- 235000014633 carbohydrates Nutrition 0.000 description 3
- 150000001735 carboxylic acids Chemical class 0.000 description 3
- 238000001816 cooling Methods 0.000 description 3
- 150000001993 dienes Chemical class 0.000 description 3
- 150000002170 ethers Chemical class 0.000 description 3
- QSHDDOUJBYECFT-UHFFFAOYSA-N mercury Chemical compound [Hg] QSHDDOUJBYECFT-UHFFFAOYSA-N 0.000 description 3
- 229910052753 mercury Inorganic materials 0.000 description 3
- 229940063559 methacrylic acid Drugs 0.000 description 3
- 125000002496 methyl group Chemical group [H]C([H])([H])* 0.000 description 3
- 125000000325 methylidene group Chemical group [H]C([H])=* 0.000 description 3
- 238000006386 neutralization reaction Methods 0.000 description 3
- 229920000915 polyvinyl chloride Polymers 0.000 description 3
- 239000011541 reaction mixture Substances 0.000 description 3
- 239000000243 solution Substances 0.000 description 3
- 230000006641 stabilisation Effects 0.000 description 3
- 238000011105 stabilization Methods 0.000 description 3
- 125000001424 substituent group Chemical group 0.000 description 3
- 150000005846 sugar alcohols Polymers 0.000 description 3
- FFJCNSLCJOQHKM-CLFAGFIQSA-N (z)-1-[(z)-octadec-9-enoxy]octadec-9-ene Chemical compound CCCCCCCC\C=C/CCCCCCCCOCCCCCCCC\C=C/CCCCCCCC FFJCNSLCJOQHKM-CLFAGFIQSA-N 0.000 description 2
- MYRTYDVEIRVNKP-UHFFFAOYSA-N 1,2-Divinylbenzene Chemical compound C=CC1=CC=CC=C1C=C MYRTYDVEIRVNKP-UHFFFAOYSA-N 0.000 description 2
- UZKWTJUDCOPSNM-UHFFFAOYSA-N 1-ethenoxybutane Chemical compound CCCCOC=C UZKWTJUDCOPSNM-UHFFFAOYSA-N 0.000 description 2
- HBXWUCXDUUJDRB-UHFFFAOYSA-N 1-octadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCCCC HBXWUCXDUUJDRB-UHFFFAOYSA-N 0.000 description 2
- OZAIFHULBGXAKX-UHFFFAOYSA-N 2-(2-cyanopropan-2-yldiazenyl)-2-methylpropanenitrile Chemical compound N#CC(C)(C)N=NC(C)(C)C#N OZAIFHULBGXAKX-UHFFFAOYSA-N 0.000 description 2
- OEPOKWHJYJXUGD-UHFFFAOYSA-N 2-(3-phenylmethoxyphenyl)-1,3-thiazole-4-carbaldehyde Chemical compound O=CC1=CSC(C=2C=C(OCC=3C=CC=CC=3)C=CC=2)=N1 OEPOKWHJYJXUGD-UHFFFAOYSA-N 0.000 description 2
- RFIMISVNSAUMBU-UHFFFAOYSA-N 2-(hydroxymethyl)-2-(prop-2-enoxymethyl)propane-1,3-diol Chemical compound OCC(CO)(CO)COCC=C RFIMISVNSAUMBU-UHFFFAOYSA-N 0.000 description 2
- KUDUQBURMYMBIJ-UHFFFAOYSA-N 2-prop-2-enoyloxyethyl prop-2-enoate Chemical compound C=CC(=O)OCCOC(=O)C=C KUDUQBURMYMBIJ-UHFFFAOYSA-N 0.000 description 2
- ATVJXMYDOSMEPO-UHFFFAOYSA-N 3-prop-2-enoxyprop-1-ene Chemical compound C=CCOCC=C ATVJXMYDOSMEPO-UHFFFAOYSA-N 0.000 description 2
- NLHHRLWOUZZQLW-UHFFFAOYSA-N Acrylonitrile Chemical compound C=CC#N NLHHRLWOUZZQLW-UHFFFAOYSA-N 0.000 description 2
- BVKZGUZCCUSVTD-UHFFFAOYSA-L Carbonate Chemical compound [O-]C([O-])=O BVKZGUZCCUSVTD-UHFFFAOYSA-L 0.000 description 2
- 101100536354 Drosophila melanogaster tant gene Proteins 0.000 description 2
- VGGSQFUCUMXWEO-UHFFFAOYSA-N Ethene Chemical compound C=C VGGSQFUCUMXWEO-UHFFFAOYSA-N 0.000 description 2
- JIGUQPWFLRLWPJ-UHFFFAOYSA-N Ethyl acrylate Chemical compound CCOC(=O)C=C JIGUQPWFLRLWPJ-UHFFFAOYSA-N 0.000 description 2
- 239000005977 Ethylene Substances 0.000 description 2
- IAYPIBMASNFSPL-UHFFFAOYSA-N Ethylene oxide Chemical group C1CO1 IAYPIBMASNFSPL-UHFFFAOYSA-N 0.000 description 2
- UFHFLCQGNIYNRP-UHFFFAOYSA-N Hydrogen Chemical group [H][H] UFHFLCQGNIYNRP-UHFFFAOYSA-N 0.000 description 2
- RRHGJUQNOFWUDK-UHFFFAOYSA-N Isoprene Chemical compound CC(=C)C=C RRHGJUQNOFWUDK-UHFFFAOYSA-N 0.000 description 2
- BAPJBEWLBFYGME-UHFFFAOYSA-N Methyl acrylate Chemical compound COC(=O)C=C BAPJBEWLBFYGME-UHFFFAOYSA-N 0.000 description 2
- 229920002415 Pluronic P-123 Polymers 0.000 description 2
- RVGRUAULSDPKGF-UHFFFAOYSA-N Poloxamer Chemical compound C1CO1.CC1CO1 RVGRUAULSDPKGF-UHFFFAOYSA-N 0.000 description 2
- OFOBLEOULBTSOW-UHFFFAOYSA-N Propanedioic acid Natural products OC(=O)CC(O)=O OFOBLEOULBTSOW-UHFFFAOYSA-N 0.000 description 2
- XTXRWKRVRITETP-UHFFFAOYSA-N Vinyl acetate Chemical compound CC(=O)OC=C XTXRWKRVRITETP-UHFFFAOYSA-N 0.000 description 2
- 230000002411 adverse Effects 0.000 description 2
- 150000001298 alcohols Chemical class 0.000 description 2
- 150000008044 alkali metal hydroxides Chemical class 0.000 description 2
- 150000001408 amides Chemical class 0.000 description 2
- 239000007864 aqueous solution Substances 0.000 description 2
- 239000007900 aqueous suspension Substances 0.000 description 2
- FUSUHKVFWTUUBE-UHFFFAOYSA-N buten-2-one Chemical compound CC(=O)C=C FUSUHKVFWTUUBE-UHFFFAOYSA-N 0.000 description 2
- 150000001719 carbohydrate derivatives Chemical class 0.000 description 2
- 229910052799 carbon Inorganic materials 0.000 description 2
- 239000004359 castor oil Substances 0.000 description 2
- 235000019438 castor oil Nutrition 0.000 description 2
- 239000011248 coating agent Substances 0.000 description 2
- 238000000576 coating method Methods 0.000 description 2
- 230000000536 complexating effect Effects 0.000 description 2
- 229920001577 copolymer Polymers 0.000 description 2
- 239000003431 cross linking reagent Substances 0.000 description 2
- DTPCFIHYWYONMD-UHFFFAOYSA-N decaethylene glycol Polymers OCCOCCOCCOCCOCCOCCOCCOCCOCCOCCO DTPCFIHYWYONMD-UHFFFAOYSA-N 0.000 description 2
- ZQMIGQNCOMNODD-UHFFFAOYSA-N diacetyl peroxide Chemical compound CC(=O)OOC(C)=O ZQMIGQNCOMNODD-UHFFFAOYSA-N 0.000 description 2
- 230000000694 effects Effects 0.000 description 2
- 125000002573 ethenylidene group Chemical group [*]=C=C([H])[H] 0.000 description 2
- LYCAIKOWRPUZTN-UHFFFAOYSA-N ethylene glycol Natural products OCCO LYCAIKOWRPUZTN-UHFFFAOYSA-N 0.000 description 2
- ZZUFCTLCJUWOSV-UHFFFAOYSA-N furosemide Chemical class C1=C(Cl)C(S(=O)(=O)N)=CC(C(O)=O)=C1NCC1=CC=CO1 ZZUFCTLCJUWOSV-UHFFFAOYSA-N 0.000 description 2
- ZEMPKEQAKRGZGQ-XOQCFJPHSA-N glycerol triricinoleate Natural products CCCCCC[C@@H](O)CC=CCCCCCCCC(=O)OC[C@@H](COC(=O)CCCCCCCC=CC[C@@H](O)CCCCCC)OC(=O)CCCCCCCC=CC[C@H](O)CCCCCC ZEMPKEQAKRGZGQ-XOQCFJPHSA-N 0.000 description 2
- 229910052736 halogen Inorganic materials 0.000 description 2
- 150000002367 halogens Chemical class 0.000 description 2
- 238000010438 heat treatment Methods 0.000 description 2
- 150000002431 hydrogen Chemical class 0.000 description 2
- VZCYOOQTPOCHFL-UPHRSURJSA-N maleic acid Chemical compound OC(=O)\C=C/C(O)=O VZCYOOQTPOCHFL-UPHRSURJSA-N 0.000 description 2
- 239000011976 maleic acid Substances 0.000 description 2
- 238000012986 modification Methods 0.000 description 2
- 230000004048 modification Effects 0.000 description 2
- YPHQUSNPXDGUHL-UHFFFAOYSA-N n-methylprop-2-enamide Chemical compound CNC(=O)C=C YPHQUSNPXDGUHL-UHFFFAOYSA-N 0.000 description 2
- QIQXTHQIDYTFRH-UHFFFAOYSA-N octadecanoic acid Chemical class CCCCCCCCCCCCCCCCCC(O)=O QIQXTHQIDYTFRH-UHFFFAOYSA-N 0.000 description 2
- PNJWIWWMYCMZRO-UHFFFAOYSA-N pent‐4‐en‐2‐one Natural products CC(=O)CC=C PNJWIWWMYCMZRO-UHFFFAOYSA-N 0.000 description 2
- HCTVWSOKIJULET-LQDWTQKMSA-M phenoxymethylpenicillin potassium Chemical compound [K+].N([C@H]1[C@H]2SC([C@@H](N2C1=O)C([O-])=O)(C)C)C(=O)COC1=CC=CC=C1 HCTVWSOKIJULET-LQDWTQKMSA-M 0.000 description 2
- 229920003023 plastic Polymers 0.000 description 2
- 239000004033 plastic Substances 0.000 description 2
- 235000011185 polyoxyethylene (40) stearate Nutrition 0.000 description 2
- 239000001194 polyoxyethylene (40) stearate Substances 0.000 description 2
- 229920002689 polyvinyl acetate Polymers 0.000 description 2
- 239000011118 polyvinyl acetate Substances 0.000 description 2
- 239000000047 product Substances 0.000 description 2
- 230000001105 regulatory effect Effects 0.000 description 2
- 238000010008 shearing Methods 0.000 description 2
- 150000004756 silanes Chemical class 0.000 description 2
- 239000002002 slurry Substances 0.000 description 2
- 229910001220 stainless steel Inorganic materials 0.000 description 2
- 239000010935 stainless steel Substances 0.000 description 2
- 235000000346 sugar Nutrition 0.000 description 2
- 238000012360 testing method Methods 0.000 description 2
- VZCYOOQTPOCHFL-UHFFFAOYSA-N trans-butenedioic acid Natural products OC(=O)C=CC(O)=O VZCYOOQTPOCHFL-UHFFFAOYSA-N 0.000 description 2
- WRXCBRHBHGNNQA-UHFFFAOYSA-N (2,4-dichlorobenzoyl) 2,4-dichlorobenzenecarboperoxoate Chemical compound ClC1=CC(Cl)=CC=C1C(=O)OOC(=O)C1=CC=C(Cl)C=C1Cl WRXCBRHBHGNNQA-UHFFFAOYSA-N 0.000 description 1
- QLLUAUADIMPKIH-UHFFFAOYSA-N 1,2-bis(ethenyl)naphthalene Chemical compound C1=CC=CC2=C(C=C)C(C=C)=CC=C21 QLLUAUADIMPKIH-UHFFFAOYSA-N 0.000 description 1
- CBXGIYSFAJVJOB-UHFFFAOYSA-N 1-[4,6-di(prop-2-enoyl)triazin-5-yl]prop-2-en-1-one Chemical compound C=CC(=O)C1=NN=NC(C(=O)C=C)=C1C(=O)C=C CBXGIYSFAJVJOB-UHFFFAOYSA-N 0.000 description 1
- LGJCFVYMIJLQJO-UHFFFAOYSA-N 1-dodecylperoxydodecane Chemical compound CCCCCCCCCCCCOOCCCCCCCCCCCC LGJCFVYMIJLQJO-UHFFFAOYSA-N 0.000 description 1
- OUUCZGCOAXRCHN-UHFFFAOYSA-N 1-hexadecoxyoctadecane Chemical compound CCCCCCCCCCCCCCCCCCOCCCCCCCCCCCCCCCC OUUCZGCOAXRCHN-UHFFFAOYSA-N 0.000 description 1
- IGGDKDTUCAWDAN-UHFFFAOYSA-N 1-vinylnaphthalene Chemical compound C1=CC=C2C(C=C)=CC=CC2=C1 IGGDKDTUCAWDAN-UHFFFAOYSA-N 0.000 description 1
- JAHNSTQSQJOJLO-UHFFFAOYSA-N 2-(3-fluorophenyl)-1h-imidazole Chemical compound FC1=CC=CC(C=2NC=CN=2)=C1 JAHNSTQSQJOJLO-UHFFFAOYSA-N 0.000 description 1
- GOXQRTZXKQZDDN-UHFFFAOYSA-N 2-Ethylhexyl acrylate Chemical compound CCCCC(CC)COC(=O)C=C GOXQRTZXKQZDDN-UHFFFAOYSA-N 0.000 description 1
- WYGWHHGCAGTUCH-UHFFFAOYSA-N 2-[(2-cyano-4-methylpentan-2-yl)diazenyl]-2,4-dimethylpentanenitrile Chemical compound CC(C)CC(C)(C#N)N=NC(C)(C#N)CC(C)C WYGWHHGCAGTUCH-UHFFFAOYSA-N 0.000 description 1
- BLXVTZPGEOGTGG-UHFFFAOYSA-N 2-[2-(4-nonylphenoxy)ethoxy]ethanol Chemical compound CCCCCCCCCC1=CC=C(OCCOCCO)C=C1 BLXVTZPGEOGTGG-UHFFFAOYSA-N 0.000 description 1
- HMENQNSSJFLQOP-UHFFFAOYSA-N 2-bromoprop-2-enoic acid Chemical class OC(=O)C(Br)=C HMENQNSSJFLQOP-UHFFFAOYSA-N 0.000 description 1
- SBYMUDUGTIKLCR-UHFFFAOYSA-N 2-chloroethenylbenzene Chemical compound ClC=CC1=CC=CC=C1 SBYMUDUGTIKLCR-UHFFFAOYSA-N 0.000 description 1
- AEPWOCLBLLCOGZ-UHFFFAOYSA-N 2-cyanoethyl prop-2-enoate Chemical compound C=CC(=O)OCCC#N AEPWOCLBLLCOGZ-UHFFFAOYSA-N 0.000 description 1
- FZHNODDFDJBMAS-UHFFFAOYSA-N 2-ethoxyethenylbenzene Chemical class CCOC=CC1=CC=CC=C1 FZHNODDFDJBMAS-UHFFFAOYSA-N 0.000 description 1
- WROUWQQRXUBECT-UHFFFAOYSA-N 2-ethylacrylic acid Chemical compound CCC(=C)C(O)=O WROUWQQRXUBECT-UHFFFAOYSA-N 0.000 description 1
- WFUGQJXVXHBTEM-UHFFFAOYSA-N 2-hydroperoxy-2-(2-hydroperoxybutan-2-ylperoxy)butane Chemical compound CCC(C)(OO)OOC(C)(CC)OO WFUGQJXVXHBTEM-UHFFFAOYSA-N 0.000 description 1
- MUHFRORXWCGZGE-KTKRTIGZSA-N 2-hydroxyethyl (z)-octadec-9-enoate Chemical compound CCCCCCCC\C=C/CCCCCCCC(=O)OCCO MUHFRORXWCGZGE-KTKRTIGZSA-N 0.000 description 1
- XLMXUUQMSMKFMH-UZRURVBFSA-N 2-hydroxyethyl (z,12r)-12-hydroxyoctadec-9-enoate Chemical compound CCCCCC[C@@H](O)C\C=C/CCCCCCCC(=O)OCCO XLMXUUQMSMKFMH-UZRURVBFSA-N 0.000 description 1
- RFVNOJDQRGSOEL-UHFFFAOYSA-N 2-hydroxyethyl octadecanoate Chemical compound CCCCCCCCCCCCCCCCCC(=O)OCCO RFVNOJDQRGSOEL-UHFFFAOYSA-N 0.000 description 1
- KGIGUEBEKRSTEW-UHFFFAOYSA-N 2-vinylpyridine Chemical compound C=CC1=CC=CC=N1 KGIGUEBEKRSTEW-UHFFFAOYSA-N 0.000 description 1
- OHXAOPZTJOUYKM-UHFFFAOYSA-N 3-Chloro-2-methylpropene Chemical compound CC(=C)CCl OHXAOPZTJOUYKM-UHFFFAOYSA-N 0.000 description 1
- UATRONWBYDQKSQ-UHFFFAOYSA-N 3-methyl-1-(3-methylbut-2-enoxy)but-2-ene Chemical compound CC(C)=CCOCC=C(C)C UATRONWBYDQKSQ-UHFFFAOYSA-N 0.000 description 1
- DBCAQXHNJOFNGC-UHFFFAOYSA-N 4-bromo-1,1,1-trifluorobutane Chemical compound FC(F)(F)CCCBr DBCAQXHNJOFNGC-UHFFFAOYSA-N 0.000 description 1
- RZVAJINKPMORJF-UHFFFAOYSA-N Acetaminophen Chemical group CC(=O)NC1=CC=C(O)C=C1 RZVAJINKPMORJF-UHFFFAOYSA-N 0.000 description 1
- HRPVXLWXLXDGHG-UHFFFAOYSA-N Acrylamide Chemical compound NC(=O)C=C HRPVXLWXLXDGHG-UHFFFAOYSA-N 0.000 description 1
- NIXOWILDQLNWCW-UHFFFAOYSA-M Acrylate Chemical compound [O-]C(=O)C=C NIXOWILDQLNWCW-UHFFFAOYSA-M 0.000 description 1
- OSDWBNJEKMUWAV-UHFFFAOYSA-N Allyl chloride Chemical compound ClCC=C OSDWBNJEKMUWAV-UHFFFAOYSA-N 0.000 description 1
- QGZKDVFQNNGYKY-UHFFFAOYSA-O Ammonium Chemical compound [NH4+] QGZKDVFQNNGYKY-UHFFFAOYSA-O 0.000 description 1
- VHUUQVKOLVNVRT-UHFFFAOYSA-N Ammonium hydroxide Chemical compound [NH4+].[OH-] VHUUQVKOLVNVRT-UHFFFAOYSA-N 0.000 description 1
- 239000004342 Benzoyl peroxide Substances 0.000 description 1
- OMPJBNCRMGITSC-UHFFFAOYSA-N Benzoylperoxide Chemical compound C=1C=CC=CC=1C(=O)OOC(=O)C1=CC=CC=C1 OMPJBNCRMGITSC-UHFFFAOYSA-N 0.000 description 1
- OKTJSMMVPCPJKN-UHFFFAOYSA-N Carbon Chemical compound [C] OKTJSMMVPCPJKN-UHFFFAOYSA-N 0.000 description 1
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- 239000000908 ammonium hydroxide Substances 0.000 description 1
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- 150000004665 fatty acids Chemical class 0.000 description 1
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- 239000011953 free-radical catalyst Substances 0.000 description 1
- 125000000524 functional group Chemical group 0.000 description 1
- YSTYFZGNKHCPQJ-UHFFFAOYSA-N furan-2,5-dione;n-methylprop-2-enamide Chemical compound CNC(=O)C=C.O=C1OC(=O)C=C1 YSTYFZGNKHCPQJ-UHFFFAOYSA-N 0.000 description 1
- 239000011521 glass Substances 0.000 description 1
- 239000008103 glucose Substances 0.000 description 1
- 229940100608 glycol distearate Drugs 0.000 description 1
- 230000005484 gravity Effects 0.000 description 1
- IPCSVZSSVZVIGE-UHFFFAOYSA-M hexadecanoate Chemical compound CCCCCCCCCCCCCCCC([O-])=O IPCSVZSSVZVIGE-UHFFFAOYSA-M 0.000 description 1
- 229920001519 homopolymer Polymers 0.000 description 1
- 150000004678 hydrides Chemical class 0.000 description 1
- 150000002432 hydroperoxides Chemical class 0.000 description 1
- XLYOFNOQVPJJNP-UHFFFAOYSA-M hydroxide Chemical compound [OH-] XLYOFNOQVPJJNP-UHFFFAOYSA-M 0.000 description 1
- 150000004679 hydroxides Chemical class 0.000 description 1
- 125000002887 hydroxy group Chemical group [H]O* 0.000 description 1
- 230000006872 improvement Effects 0.000 description 1
- 239000003112 inhibitor Substances 0.000 description 1
- CDAISMWEOUEBRE-GPIVLXJGSA-N inositol Chemical compound O[C@H]1[C@H](O)[C@@H](O)[C@H](O)[C@H](O)[C@@H]1O CDAISMWEOUEBRE-GPIVLXJGSA-N 0.000 description 1
- 229960000367 inositol Drugs 0.000 description 1
- 230000003993 interaction Effects 0.000 description 1
- 150000002576 ketones Chemical class 0.000 description 1
- 150000002596 lactones Chemical class 0.000 description 1
- 239000004816 latex Substances 0.000 description 1
- 229920000126 latex Polymers 0.000 description 1
- 229940070765 laurate Drugs 0.000 description 1
- 239000007788 liquid Substances 0.000 description 1
- 239000000594 mannitol Substances 0.000 description 1
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- 230000007246 mechanism Effects 0.000 description 1
- HEBKCHPVOIAQTA-UHFFFAOYSA-N meso ribitol Natural products OCC(O)C(O)C(O)CO HEBKCHPVOIAQTA-UHFFFAOYSA-N 0.000 description 1
- 229910052751 metal Inorganic materials 0.000 description 1
- 239000002184 metal Substances 0.000 description 1
- LVHBHZANLOWSRM-UHFFFAOYSA-N methylenebutanedioic acid Natural products OC(=O)CC(=C)C(O)=O LVHBHZANLOWSRM-UHFFFAOYSA-N 0.000 description 1
- 238000002156 mixing Methods 0.000 description 1
- ZIUHHBKFKCYYJD-UHFFFAOYSA-N n,n'-methylenebisacrylamide Chemical compound C=CC(=O)NCNC(=O)C=C ZIUHHBKFKCYYJD-UHFFFAOYSA-N 0.000 description 1
- 229940088644 n,n-dimethylacrylamide Drugs 0.000 description 1
- YLGYACDQVQQZSW-UHFFFAOYSA-N n,n-dimethylprop-2-enamide Chemical compound CN(C)C(=O)C=C YLGYACDQVQQZSW-UHFFFAOYSA-N 0.000 description 1
- KKFHAJHLJHVUDM-UHFFFAOYSA-N n-vinylcarbazole Chemical compound C1=CC=C2N(C=C)C3=CC=CC=C3C2=C1 KKFHAJHLJHVUDM-UHFFFAOYSA-N 0.000 description 1
- VIDGELNFXVPECZ-UHFFFAOYSA-N naphthalene-1-carbonyl naphthalene-1-carboperoxoate Chemical compound C1=CC=C2C(C(OOC(=O)C=3C4=CC=CC=C4C=CC=3)=O)=CC=CC2=C1 VIDGELNFXVPECZ-UHFFFAOYSA-N 0.000 description 1
- GSGDTSDELPUTKU-UHFFFAOYSA-N nonoxybenzene Chemical compound CCCCCCCCCOC1=CC=CC=C1 GSGDTSDELPUTKU-UHFFFAOYSA-N 0.000 description 1
- 229940065472 octyl acrylate Drugs 0.000 description 1
- ANISOHQJBAQUQP-UHFFFAOYSA-N octyl prop-2-enoate Chemical compound CCCCCCCCOC(=O)C=C ANISOHQJBAQUQP-UHFFFAOYSA-N 0.000 description 1
- 125000001117 oleyl group Chemical group [H]C([*])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])/C([H])=C([H])\C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])C([H])([H])[H] 0.000 description 1
- WXZMFSXDPGVJKK-UHFFFAOYSA-N pentaerythritol Chemical compound OCC(CO)(CO)CO WXZMFSXDPGVJKK-UHFFFAOYSA-N 0.000 description 1
- 125000000864 peroxy group Chemical group O(O*)* 0.000 description 1
- 239000012071 phase Substances 0.000 description 1
- 239000004999 plastisol Substances 0.000 description 1
- 229920001983 poloxamer Polymers 0.000 description 1
- 229920000233 poly(alkylene oxides) Polymers 0.000 description 1
- 229920002857 polybutadiene Polymers 0.000 description 1
- 229920000728 polyester Polymers 0.000 description 1
- 239000002685 polymerization catalyst Substances 0.000 description 1
- 229920005862 polyol Polymers 0.000 description 1
- 150000003077 polyols Chemical class 0.000 description 1
- 235000010486 polyoxyethylene sorbitan monolaurate Nutrition 0.000 description 1
- 235000010482 polyoxyethylene sorbitan monooleate Nutrition 0.000 description 1
- 229920001451 polypropylene glycol Polymers 0.000 description 1
- 229920000053 polysorbate 80 Polymers 0.000 description 1
- 238000012545 processing Methods 0.000 description 1
- QTECDUFMBMSHKR-UHFFFAOYSA-N prop-2-enyl prop-2-enoate Chemical compound C=CCOC(=O)C=C QTECDUFMBMSHKR-UHFFFAOYSA-N 0.000 description 1
- HJWLCRVIBGQPNF-UHFFFAOYSA-N prop-2-enylbenzene Chemical compound C=CCC1=CC=CC=C1 HJWLCRVIBGQPNF-UHFFFAOYSA-N 0.000 description 1
- BWJUFXUULUEGMA-UHFFFAOYSA-N propan-2-yl propan-2-yloxycarbonyloxy carbonate Chemical compound CC(C)OC(=O)OOC(=O)OC(C)C BWJUFXUULUEGMA-UHFFFAOYSA-N 0.000 description 1
- YPVDWEHVCUBACK-UHFFFAOYSA-N propoxycarbonyloxy propyl carbonate Chemical compound CCCOC(=O)OOC(=O)OCCC YPVDWEHVCUBACK-UHFFFAOYSA-N 0.000 description 1
- 238000005086 pumping Methods 0.000 description 1
- MUPFEKGTMRGPLJ-ZQSKZDJDSA-N raffinose Chemical compound O[C@H]1[C@H](O)[C@@H](CO)O[C@@]1(CO)O[C@@H]1[C@H](O)[C@@H](O)[C@H](O)[C@@H](CO[C@@H]2[C@@H]([C@@H](O)[C@@H](O)[C@@H](CO)O2)O)O1 MUPFEKGTMRGPLJ-ZQSKZDJDSA-N 0.000 description 1
- 230000009467 reduction Effects 0.000 description 1
- CDAISMWEOUEBRE-UHFFFAOYSA-N scyllo-inosotol Natural products OC1C(O)C(O)C(O)C(O)C1O CDAISMWEOUEBRE-UHFFFAOYSA-N 0.000 description 1
- 239000000344 soap Substances 0.000 description 1
- HPALAKNZSZLMCH-UHFFFAOYSA-M sodium;chloride;hydrate Chemical compound O.[Na+].[Cl-] HPALAKNZSZLMCH-UHFFFAOYSA-M 0.000 description 1
- 235000011071 sorbitan monopalmitate Nutrition 0.000 description 1
- 239000001570 sorbitan monopalmitate Substances 0.000 description 1
- 229940031953 sorbitan monopalmitate Drugs 0.000 description 1
- 235000019337 sorbitan trioleate Nutrition 0.000 description 1
- 229960000391 sorbitan trioleate Drugs 0.000 description 1
- 239000001589 sorbitan tristearate Substances 0.000 description 1
- 235000011078 sorbitan tristearate Nutrition 0.000 description 1
- 229960004129 sorbitan tristearate Drugs 0.000 description 1
- 239000000600 sorbitol Substances 0.000 description 1
- 235000010356 sorbitol Nutrition 0.000 description 1
- 229960002920 sorbitol Drugs 0.000 description 1
- 239000012798 spherical particle Substances 0.000 description 1
- 150000003440 styrenes Chemical class 0.000 description 1
- 239000000126 substance Substances 0.000 description 1
- 238000003786 synthesis reaction Methods 0.000 description 1
- NMOALOSNPWTWRH-UHFFFAOYSA-N tert-butyl 7,7-dimethyloctaneperoxoate Chemical compound CC(C)(C)CCCCCC(=O)OOC(C)(C)C NMOALOSNPWTWRH-UHFFFAOYSA-N 0.000 description 1
- GJBRNHKUVLOCEB-UHFFFAOYSA-N tert-butyl benzenecarboperoxoate Chemical compound CC(C)(C)OOC(=O)C1=CC=CC=C1 GJBRNHKUVLOCEB-UHFFFAOYSA-N 0.000 description 1
- 230000008719 thickening Effects 0.000 description 1
- LDHQCZJRKDOVOX-UHFFFAOYSA-N trans-crotonic acid Natural products CC=CC(O)=O LDHQCZJRKDOVOX-UHFFFAOYSA-N 0.000 description 1
- KOZCZZVUFDCZGG-UHFFFAOYSA-N vinyl benzoate Chemical compound C=COC(=O)C1=CC=CC=C1 KOZCZZVUFDCZGG-UHFFFAOYSA-N 0.000 description 1
- ORGHESHFQPYLAO-UHFFFAOYSA-N vinyl radical Chemical class C=[CH] ORGHESHFQPYLAO-UHFFFAOYSA-N 0.000 description 1
- 229920003176 water-insoluble polymer Polymers 0.000 description 1
Classifications
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F2/00—Processes of polymerisation
- C08F2/12—Polymerisation in non-solvents
- C08F2/16—Aqueous medium
- C08F2/22—Emulsion polymerisation
- C08F2/24—Emulsion polymerisation with the aid of emulsifying agents
- C08F2/30—Emulsion polymerisation with the aid of emulsifying agents non-ionic
-
- C—CHEMISTRY; METALLURGY
- C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
- C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
- C08F14/00—Homopolymers and copolymers of compounds having one or more unsaturated aliphatic radicals, each having only one carbon-to-carbon double bond, and at least one being terminated by a halogen
- C08F14/02—Monomers containing chlorine
- C08F14/04—Monomers containing two carbon atoms
- C08F14/06—Vinyl chloride
Definitions
- polymer particles produced in accordance with these processes are not uniform in size and shape. This is due, in most instances, to the instability of the monomer dis ⁇ persion which causes agglomeration of the polymerizing particles.
- polymers such as, for example, polyvinyl chloride (PVC)
- PVC polyvinyl chloride
- the polymer ⁇ ization reaction is then carried out using a batch or continuous process under substantially quiescent con ⁇ ditions, that is, in the absence of turbulence or the absence of shearing forces sufficient to deform the suspended droplets of monomer and/or to damage the poly ⁇ mer bead at any stage of conversion.
- substantially quiescent con ⁇ ditions that is, in the absence of turbulence or the absence of shearing forces sufficient to deform the suspended droplets of monomer and/or to damage the poly ⁇ mer bead at any stage of conversion.
- the uni ⁇ form beads of PVC that are formed are normally clear and glassy in nature and do not have the desired porosity, which is desirable in subsequent operations involving th finished polymer.
- porous polymer particles or beads are desirable, such as where the polymer, such as PVC, is to be employed in making plast- isols and in extrusion operations. Porous beads would also be desirable in the case of PVC where, because of Government regulations, it is necessary to remove sub ⁇ stantially all of the unreacted vinyl chloride therefrom Porous polymer beads or particles would greatly facili ⁇ tate such removal.
- a dispersion or emulsion comprised of the monomer or monomers to be polymerized, a surfac ⁇ tant, or surfactant system, and a monomer-soluble free radical yielding polymerization catalyst, in an aqueous medium containing a water-insoluble suspending or disper ⁇ sing agent comprising an unneutralized cross-linked inter- polymer of one or more carboxylic acid monomers with a polyunsaturated compound having a plurality of termin ⁇ ally unsaturated polymerizable groups.
- Said dispersion is formed using high agitation at a temperature below the reaction temperature of the catalyst.
- the disper ⁇ sion is partially neutralized with an alkali and then polymerized with stirring to a conversion of about 10% to about 30%, said stirring being substantially less than that used in making the dispersion and then continuing the reaction to completion with increased stirring but no greater than that used in making the dispersion.
- the resultant polymer particles are non-agglomerated, spher ⁇ ical, highly porous and have the same size distribution as the original liquid dispersion.
- vinyl halides and vinylidene halides such as vinyl bro- mide, vinyl fluoride, vinylidenechloride, etc.
- vinyl ⁇ idene monomers having at least one terminal ing, such as acrylic acid, methacrylic acid, acrylo- nitrile, vinyl acetate, and the like; esters of acrylic acid, for example, methyl, acrylate, ethyl acrylate, butyl acrylate, octyl acrylate, cyanoethyl acrylate, and the like; esters of methacrylic acid, such as methyl rnethacrylate, ethyl rnethacrylate, butyl rnethacrylate, and the like; styrene and styrene derivatives including -methyl styrene, vinyl toluene, chlorostyrene; vinyl naphthalene; diolefins including butadiene,
- the monomer-soluble or oil-soluble catalysts that may be used in the polymerization process of the present invention are the alkanoyl, aroyl, alkaroyl, aralkanoyl diperoxides and monohydroperoxides, azo compounds, peroxy esters, percarbonates, and other free radical type catalysts.
- Such catalysts there may be named benzoyl peroxide, lauryl peroxide, diacetyl peroxide, cu ene hydroperoxides, methyl ethyl ketone peroxide, diisopropylbenzene hydroperoxide, 2,4- dichlorobenzoyl peroxide, naphthoyl peroxide, t-butyl perbenzoate, di-t-butyl perphthalate, isopropyl percar- bonate, acetyl cyclohexane sulfonyl peroxide, di-secon- dary butyl peroxydicarbonate, t-butyl peroxyneodecanoate, di-normal propyl peroxydicarbonate, azo-bis-isobutyroni- trile, ⁇ ''-azo&xisobutyrate, 2,2'-azo-bis-(2,4-dimethyl valeronitrile) , and many
- the particular free radical catalyst employed will depend upon the monomer(s) being polymerized, the molecular weight and color re ⁇ quirements of the polymer, the temperature of polymeri- zation, etc. Insofar as the amount of catalyst employed is concerned, it has been found that an amount in the range of about 0.005% to about 1.0% by weight, based on the weight of the monomer or monomers being polymerized, is satisfactory. However, it is preferred to employ an amount of catalyst in the range of about 0.01% to about 0.20% by weight.
- the water-insoluble suspending or dispersing agent employed is an unneutralized crosslinked inter-
- OMPI polymer of one or more carboxylic acid monomers with a polyunsaturated compound having a plurality of termi ⁇ nally unsaturated polymerizable groups for example, a crosslinked polyacrylic acid polymer.
- the crosslink- 5 ing is necessary since an uncrosslinked polyacrylic aci polymer will produce a highly agglomerated charge, that is, due to an unstable environment, the polymer particl coalesce producing the agglomerates. Due to the cross- linking the interpolymerare incapable of forming a true
- the viscosity of the polymeriza ⁇ tion medium can be regulated by adjusting the amount of suspending or dispersing agent added thereto and its
- the minimum yield value required in aqueous polymerization medium for suspension stability with any given monomeric material depends on several factors, namely, (1) the density difference between the mono ⁇ meric and aqueous phases, labeled D-D and expressed as grams/cm. ; (2) the desired or actual radius (R) of the suspended monomer droplet, expressed in cm. ; and
- Yield Value (BYV) for permanent suspension can be cal ⁇ culated by the formula:
- BYV values are measured or calcu ⁇ lated from rheological data obtained by the use of the Brookfield RVT Viscometer, operated at the temperature to be utilized in the polymerization, whereby one measures the Brookfield apparent viscosity (BAV) in centipoises at 0.5 rp . and at 1.0 rpm. If these data are plotted against shear rate and the curve* extrapola- ted to zero shear rate, the BYV is obtained directly. However, the minimum BYV for permanent stability can be approximated rom the formula:
- a useful and easily measured and calculated viscometric parameter is the ratio (R * )
- BYV values with the suspending or dispersing agents of the present invention will be, at a minimum, in the range of about 20 to about 50 for the usual monomers and particle sizes. Most often, wit many of these monomers, the practical operating range will be from about 50 to about 120.
- the Brookfield apparent viscosity at 20 rpm. of the polymerization media of such BYV will be in the range of about 760 to about 1500 centipoises .
- the carboxylic acid monomers, which are use ful in preparing the crosslinked polymeric dispersing or suspending agents, are those which contain at least one active carbon to carbon double bond in the ⁇ , ⁇ -positio with respect to a carboxyl group having the formula R"R" '
- each of R" and R" ' is a hydrogen or a monovalent substituent group which is linked to one of the doubly bonded carbon atoms
- Carboxylic acids within this definition include acids , such as acrylic and, wherein the double bond is terminal thusly
- R and R ! are monovalent substituent groups and especially those selected from the group consisting of hydrogen, halogen, alkyl, aryl, alkaryl, aralkyl, and cycloaliphatic radicals.
- carboxylic acids include acrylic acid itself, meth- acrylic acid, ethacrylic acid, ⁇ -and ⁇ -chloro- and bromo- acrylic acids, crotonic acid, maleic acid, itaconic acid, and many others.
- Polymerizable carboxylic anhydrides include any of the anhydrides of the above acids, including mixed anhydrides, and those shown by generic formula (C) above, including maleic anhydride, and others. In many cases it is perferred to copolymerize an anhy ⁇ dride monomer with a comonomer, such as methyl vinyl ether, styrene, and the like. In the present invention, it is preferred to employ polymeric suspending agents which are derived from polymers produced by the polymerization of the ⁇ ⁇ - monoolefinically unsaturated carboxylic acids.
- the pre ⁇ ferred carboxylic acids are those derived from the acry- lie acids and ⁇ -substituted acrylic acids having the general formula
- (d)CH 2 C-C00H
- R is a monovalent substituent selected from the group consisting of hydrogen, halogen, hydroxyl, carbox- yl, amide, ester, lactone, and lacta groups.
- the most preferred polymeric suspending agents are those prepared from the lightly crosslinked interpolymers of acrylic acid since these are the most efficient.
- the crosslinking agents which may be employed with any of the carboxylic monomers, or mixtures thereof, may be any compound, not necessarily monomeric in nature, containing two or more terminal polymerizable groups per molecule. Examples of this class of materials include polyunsatur ted ⁇ hydrocarbons, -polyethers, -polyesters, -nitriles, -acids, -acid an ⁇ hydrides, -ketones, -alcohols and polyunsaturated com ⁇ pounds of this class incorporating one or more of these and other functional groups.
- divinyl benzene divinyl naphthalene
- low molecular weight and soluble polymerized dienes such as, polybutadiene and other soluble homopolymers of open chain aliphatic conjugated dienes, which soluble polymers do not contain any appreciable number of con ⁇ jugated double bonds, and other polyunsaturated hydro ⁇ carbons
- polyunsaturated esters, ester-amides and other ester derivatives such as ethylene glycol diacrylate, ethylene glycol dimethacrylate, allyl acrylate, methy- lene bis-acrylamide, methylene bismethac.rylamide, tri- acrylyl triazine, hexallyl tri ethylene trisulfone and many others
- polyunsaturated ethers such as divinyl ether, diallyl ether, dimethyl allyl ether, diallyl ethylene glycol ether, diallyl, triallyl and other poly allyl ether
- silanes and others.
- the polyalkenyl polyethers of the carbohydrate sugars, sugar alcohols, and other poly ⁇ hydroxy carbohydrate type derivatives containing from 2 to 7 alkenyl ether groups per molecule are particularly useful. Such materials are easily prepared by a
- Williamson-type synthesis involving the reaction of an alkenyl halide, such as allyl chloride, allyl bromide, methallyl chloride, ⁇ rotyl chloride, and the like, with a strongly alkaline solution of one or more of the polyhydroxy carbohydrate derivatives.
- an alkenyl halide such as allyl chloride, allyl bromide, methallyl chloride, ⁇ rotyl chloride, and the like
- the two essential monomeric materials should be present in certain proportions, although the exact proportions will vary considerably depending on the characteristics de ⁇ sired in the polymer.
- Useful dis ⁇ persing agents are also obtained when 0.1% to 6.0%, and preferably 0.2% to 5.0%, by weight of the polyether is copolymerized with maleic anhydride. In the dual co- polymer, or two-componenet interpolymer, this means that the remainder of the monomeric mixture will be the car ⁇ boxylic monomer.
- the monomeric proportions employed in the production of multi-component interpolymers may vary in a somewhat similar manner. However, it is generally de ⁇ sirable to utilize as much of the carboxylic monomer or monomers and as little of the other monomeric constit ⁇ uents as is consistent with the desired water-insolu ⁇ bility and other properties. In these interpolymers, therefore, the carboxylic monomer or monomers should never be less than 25%, and preferably not less than 40%, by weight of the total monomeric mixture.
- Multi-com ⁇ ponent interpolymers may be made from monomeric mixtures comprising from 25% to 95% of a carboxylic monomer, such as acrylic acid, 0.1% to 30% of a polyalkenyl polyether, such as polyallyl polyether of sucrose, and 5.0% to 74.9% of an additional monomer or monomers.
- a carboxylic monomer such as acrylic acid
- a polyalkenyl polyether such as polyallyl polyether of sucrose
- Preferred multi-componenet interpolymers are the tripolymers re ⁇ sulting from .the polymerization of monomeric mixtures containing, respectively, from 40% to 95% by weight of acrylic acid, 0.20% to 2.5% by weight of polyallyl poly ⁇ ether, such as that of sucrose, and 4% to 59% of an additional monomer or monomers, such as maleic anhydride N-methyl acrylamide, methyl vinyl ether, etlryl vinyl ether, n-butyl vinyl ether, and the like, and mixtures of maleic anhydride, a vinyl alkyl ether, such as vinyl methyl ether, and a polyallyl polyether, in which the sum of the moles of vinyl ether and polyallyl polyether is substantially equivalent to the molar quantity of maleic anhydride present.
- an additional monomer or monomers such as maleic anhydride N-methyl acrylamide, methyl vinyl ether, etlryl vinyl ether, n-butyl vinyl ether, and
- Suitable for use as additional monomers in the production of multi-component interpolymers are mono olefinic vinylidene monomers containing one terminal group, such as styrene, the chloro- and ethoxy- styrenes, etc., acrylamide, N-methyl-acrylamide, N,N- dimethyl acrylamide, acrylonitrile, methacrylonitrile, methyl acrylate, ethyl acrylate, 2-ethylhexylacrylate, methyl rnethacrylate, vinyl acetate, vinyl benzoate, vinyl pyridine, vinyl chloride, vinylidene chloride, vinylidene chlorobromide,.
- vinyl carbazole vinyl pyrr- olidone, methyl vinyl ether, ethyl vinyl ether, n-butyl vinyl ether, methyl vinyl ketone, ethylene, isobutylene, dimethyl maleate, diethyl maleate, and many others.
- many of the divinyl dialkenyl or other polyfunctional esters, amides, ethers, ketones, and the like may be used in the pro ⁇ duction of multi-component interpolymers, especially those polyfunctional monomers which nominally function as crosslinking or insolubilizing monomers.
- N-methyl acrylamide, methyl vinyl ether, ethyl vinyl ether and divinyl ether have ,been found particularly useful in the production of the unneutralized crosslinked interpolymers for use as water- insoluble suspending agents in the polymerization pro ⁇ cess of the instant invention.
- surfactant or surfactant system One important aspect of the present inven ⁇ tion is the choice of surfactant or surfactant system. It is necessary that the surfactant or surfactants cho- sen.for use in the invention be such that at least one of the surfactants contain one or more poly(ethylene oxide) (PEO) segments. It has been found that the water-insoluble crosslinked suspending agent in the reaction medium is an indispensable part of the surfac- tant system. The ability of the surfactant to prevent
- surfactants useful for the pur ⁇ pose of preventing the monomer droplets from coalescing are those falling within the following generic classes: (1) polyoxyethylene alkylphenols; (2) polyoxyethylene alcohols; (3) polyoxyethylene esters of fatty acids; (4) polyoxyethylene alkylamines; (5) polyoxyethylene alkylamides; and (6) polyalkylene oxide block copolymer
- surfactants in the above-named classes there may be named the following: polyoxyethylene (20) sorbitan monooleate, polyoxyethylene (20) sorbitan mono laurate, polyoxyethylene (20) sorbitan monopalmitate, polyoxyethylene (20) sorbitan monostearate, polyoxyethy lene (40) stearate, polyoxyethylene (50) stearate, polyoxyethylene esters of mixed fatty and resin acids, polyoxyethylene (20) palmitate, polyethylene glycol monolaurate, polyethylene glycol monooleate, polyethy ⁇ lene glycol ricinoleate, polyethylene
- block copolymer surfactants is the family of surfactants manufactured by BASF/Wyandotte and sold under the trade- mark "Pluronic". These surfactants are polyethylene oxide - polypropylene oxide block copolymers and have the following general formula:
- Surfactants other than the essential poly ⁇ ethylene oxide-containing materials referred to above, may also be added to the reaction mixture for the pur ⁇ pose of improving the porosity of the vinyl resin par ⁇ ticles or for otherwise modifying or controlling the internal structure, or skin structure, of the vinyl resin particles.
- Surfactants employed for this purpose are chosen on the basis of their Hydrophile-Lipophile
- HLB Hydrolyzed Polyvinyl acetate
- useful surfac- tants are those compounds from the sorbitan ester family or the polyol families, as well as the polyvinyl ⁇ alcohols, which do not contain polyethylene oxide seg ⁇ ments.
- surfactants there may be named sorbitan trioleate, sorbitan tristearate, sorbit monooleate, sorbitan monopalmitate, Alcotex®, which is 72.5% hydrolyzed polyvinyl acetate, and the like.
- the satisfactory surfactants for improving the vinyl resin porosity and internal structure of the polymer particle will have an HLB in the range of about 2 to about 19 and preferably an HLB in the range of about 2 to about 6.
- These surfactants which are added to enhance mon ⁇ omer droplet stabilization and polymer particle por ⁇ osity, can be employed in any relative amounts so long as the polyethylene oxide containing surfactant is added within the ranges specified hereinabove.
- a skin is formed around the polymer particle. • However, this skin is so thin that plasticizers can penetrate it when making polymer compounds.
- the emulsification procedure affects only the resistance to droplet sticking and this difference in emulsification procedure is not important unless the reaction is a stirred one, such as in the process of the present invention.
- a quies ⁇ cent reaction such as described in U..S. Patent No. 3,620,988, the monomer droplets are suspended by the mucilage and do not collide with each other so that the necessity of preventing monomer droplet sticking does not arise.
- the choice of the neutralization procedure in the present inven ⁇ tion is critical in order to attain the desired objec ⁇ tives.
- alkali metal hydroxides may be employed, such as potassium hydroxide, lithium hydroxide, and the like, and also ammonium hydroxide. It is preferable to add the hydroxides to the emulsion or polymerization med ⁇ ium, after emulsification is complete, by means of an aqueous solution thereof. Satisfactory solutions are those containing from about 1.0% to about 50.0% by weight of the alkali metal hydroxide or ammonium hydro ⁇ xide.
- an aqueous solution containing from about 10.0% to about 25.0% of the hydroxide is employed
- Another very important aspect of the pre ⁇ sent invention is the type and amount of agitation, or stirring employed, both in forming the polymerization recipe emulsion and during the reaction thereof.
- all of the ingredients of the polymerization recipe Prior to the start of the polymerization reaction, all of the ingredients of the polymerization recipe are agitated or stirred to form an emulsion or dispersion wherein sufficient shear action is used to disperse or suspend the monomer(s) in the reaction medium in the form of tiny droplets. This is referred to as the first stage of agitation.
- the droplets of monomer(s) should be of such size that when transformed into polymer particles,
- the polymer particles produced in accord ⁇ ance with the present invention should have a diameter in the range of about 30 microns to about 1000 microns. Preferably, for most end uses, the polymer particles will have a diameter in the range of about 80 microns to about 300 microns.
- the reaction vessel or polymerizer is made of stainless steel or glass lined and fitted with a heating and cool ⁇ ing jacket and having a rotatable shaft mounted centrally thereof. On said shaft are mounted one or more three- pronged agitator blades, the prongs of which are prefer- ably curved and pitched, that is, are contoured. Of course, blades with more or less than three prongs may be used.
- baffles are mounted internally of the reaction vessel which gives an * up and down, or pumping, action to the reaction medium in addition to the circular motion thereof.
- One or more baffles are employed mounted on the inner wall of the reactor or adjacent thereto.
- the amount and manner of agitation desired or necessary to obtain the desired results will vary depending upon the particular monomer or monomers being polymerized. Also, the particular polymer particle size desired in the end product. This means that the rpm. of the rotatable shaft carrying the agitator blades must be regulated within certain prescribed limits. There are many variables involved in obtaining the optimum con ⁇ ditions for any particular polymerization recipe, such
- OMPI WIPO as, for example, the size of the reactor, the number- of blades and prongs thereon, as well as the shape thereof, which will dictate the rpm. to be employed in obtaining the desirable particle size, as well as the desired porosity of the polymer particles.
- a polymerization reactor having a capacity of about 30 gallons, an rpm., with a plurality of agi ⁇ tator blades, such as one of the Pfaudler type, in the range of about 60 rpm. to about 150 rpm. is satisfac- tory.
- the agitation and shear action will also be influenced by the monomer(s) being poly ⁇ merized and the temperature of the polymerization re ⁇ action. In the present invention, it is not only important to choose the proper agitation, or proper rpm. but the agitation is done in stages wherein the rpm. varies in each stage. This can be referred to as agi ⁇ tation ramping of a sort.
- the first stage of agitation is that of forming the disper ⁇ sion or emulsion of the ingredients prior to the start of polymerization.
- agitation or stirring is employed but at a rate lower than the first stage.
- the second stage commences with the start of the polymerization reaction and continues until a conversion of monomer(s) to polymer of about 10.0% to about 30.0%.
- the stirring is increased but the rate is not above the rate of stirring in the first stage.
- the third stage continues to completion of the reaction which will be a total conversion of about 60.0% to about 90.0%.
- the range of rpm. of the agitator in the first stage, wherein the polymerization dispersion or emulsion is formed, using a Pfaudler or like agitator, has been set out above.
- the rpm. of the agitator will be in the range of 0 rpm. to about 1/4 of the rpm employed in the first stage.
- the rpm. will be in the range of 0 rpm. to a maximum which is equal to the rpm. employed in the first stage.
- an rpm. of 600 will be used in the first stage
- an rpm. of 70 is used in the second stage from 0% to 30% conversion
- an rpm. of 400 is used in the third stage from 30% to 70% conversion, or completion of the reaction.
- the polymer particles produced have an average particle size and size distribution substantially the same as corresponding polymers made quiescently.
- the polymer particles of the instant invention have a substantially higher porosity than the quies- cently produced polymers.
- a quiescently produced polymer had a porosity, measured with a mercury porosimeter of 0_1052 ⁇ ./gm. at 86% con- version while a polymer, produced using stirring at 1 rpm. up to 30% conversion and then at 50 rpm. to 86% conversion, had a porosity of 0.2213 cc./gm. Similar results have always been obtained regardless of the surfactant system employed.
- the polymerization process of the present invention may be carried out at any temperature which is normal for the monomeric material to be polymerized. Usually, a temperature in the range of about 30°C. to about 100°C. will be employed with most known poly- merizable monomeric materials, as set out hereinabove. Preferably, a temperature in the range of about 40°C. to about 70°C. is employed.
- the temperature is con ⁇ trolled during the polymerization process by keeping the reaction medium in contact with cooling surfaces. This is accomplished by passing a cooling medium, such as water, brine, and the like, through the jacket surround ⁇ ing the reaction vessel or polymerizer. The cooling is necessary since most all of the polymerization reactions are exothermic in nature. It is understood, of course, that, where necessary, a heating medium can be circul ⁇ ated through the jacket.
- a rating scale has been devised with res ⁇ pect to paper and sandy buildup.
- the reactor is given a rating of 1.5. Any rating below 1.0 is good or a def ⁇ inite improvement. In other words, a rating of 0.0 is perfect, and so on.
- Pluronic L-61 Ole- Soluble 0 . 50
- the temperature was raised to the reaction temperature (55°C.) and the sodium hydroxide was inject ⁇ ed into the reactor. Thereafter the agitator speed was reduced to 70 rpm. and held there until 20-30% conver ⁇ sion was reached. Then the agitator speed was increased to 400 rpm. and held there until completion of the reac ⁇ tion or 70% conversion.
- the dispersant in water mixture was continuously added to the reactor as the volume de ⁇ creased due to formation of polymer in order to keep the reactor full.
- the time of reaction was 4.5 hours at which time the reactor was cooled rapidly and the poly ⁇ mer slurry removed.
- the pH of the slurry was 5.1.
- the reactor was examined for polymer buildup with the follow ing rating: Paper buildup 0,9 and Sandy buildup 0.9. Tests were run on the recovered and dried polymer with the following results:
- P. owder mix time is the time in seconds it takes the dry polymer to absorb plasticizer.
- the porosity was measured with a mercury porosimeter.
- the polymer produced was spherical and unagglomerated.
- Example II In this example ' two runs were made using the same recipe in order to compare the porosity of the polymer particles when produced by the present inven ⁇ tion and when produced quiescently, i.e. , without stirring.
- the recipe used was as follows:
- Example I The procedure of Example I was followed except for the agitation. In both runs the agitator was operated at 600 rpm. to emulsify the vinyl chloride into the proper droplet size. In one run (quiescent) the agitation was stopped at the beginning of the reaction and no further stirring was employed. In the other run, the agitator was run a 1 rpm. up to 30% conversion and then
- the porosity was substantially higher (over 100% higher) when using invention.
- Nonylphenoxy poly (15) ethyleneoxy ethanol.
- Example II (4) "y 72.5% hydrolyzed polyvinyl acetate.
- the procedure of Example I was followed except for the agitation.
- the agitator was operated at 600 rpm. to emulsify the vinyl chloride.
- the agitator speed was ad- justed to 50 rpm. until 20% conversion was reached.
- Run No. 2 The only difference in Run No. 2 was that the agitator was operated at 400 rpm. during emulsification and at 65 rpm. in the second stage.
- the reactor was examined, in each case, upon completion of the reaction to deter ⁇ mine the polymer buildup.
- the powder mix time of the polymers was measured and the results were as follows: Run No. ' 1 2 Buildup
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Abstract
Description
Claims
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
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US15106080A | 1980-05-19 | 1980-05-19 | |
US151060 | 1988-02-01 |
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EP0051678A1 EP0051678A1 (en) | 1982-05-19 |
EP0051678A4 true EP0051678A4 (en) | 1982-11-25 |
EP0051678B1 EP0051678B1 (en) | 1986-09-03 |
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EP (1) | EP0051678B1 (en) |
JP (1) | JPH048442B2 (en) |
BE (1) | BE888865A (en) |
BR (1) | BR8108609A (en) |
CA (1) | CA1206298A (en) |
ES (1) | ES502333A0 (en) |
GR (1) | GR75231B (en) |
IN (1) | IN151754B (en) |
IT (1) | IT1136602B (en) |
MX (1) | MX158979A (en) |
PT (1) | PT73055B (en) |
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US4419502A (en) * | 1982-09-29 | 1983-12-06 | The B. F. Goodrich Company | Polymerization process for carboxyl containing polymers |
US4668730A (en) * | 1985-08-05 | 1987-05-26 | National Starch And Chemical Corp. | Colloid stabilized latex adhesives |
US4721748A (en) * | 1985-08-05 | 1988-01-26 | National Starch And Chemical Corporation | Colloid stabilized latex adhesives |
TWI782804B (en) * | 2021-11-30 | 2022-11-01 | 臺灣塑膠工業股份有限公司 | Polyvinyl chloride and method for producing the same |
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IT643255A (en) * | 1960-12-30 | |||
US3340243A (en) * | 1962-07-10 | 1967-09-05 | Monsanto Co | Aqueous suspension polymerization of vinyl chloride in presence of a nonionic, water soluble, hydrophilic colloid and an acyl persulfonate |
US3423352A (en) * | 1965-06-04 | 1969-01-21 | Celanese Corp | Method of preparation of vinyl acetate copolymer latex |
US3706722A (en) * | 1967-05-29 | 1972-12-19 | Dow Chemical Co | Polymers from essentially water-insoluble unsaturated liquid monomers and process for preparing same |
US3620988A (en) * | 1968-10-31 | 1971-11-16 | Goodrich Co B F | Method of preparing bead-type polymers |
US3907730A (en) * | 1973-09-27 | 1975-09-23 | Goodrich Co B F | Resinous initiator suspension for olefinic polymerization reactions |
GB1518852A (en) * | 1975-07-28 | 1978-07-26 | Ici Ltd | Disperse monoazo nitro thiazole dyestuffs |
DE2629467A1 (en) * | 1976-06-30 | 1978-01-05 | Wacker Chemie Gmbh | Aqueous CATALYST CONFECTION |
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- 1981-05-07 WO PCT/US1981/000611 patent/WO1981003333A1/en active IP Right Grant
- 1981-05-07 EP EP81901640A patent/EP0051678B1/en not_active Expired
- 1981-05-07 JP JP56502097A patent/JPH048442B2/ja not_active Expired
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- 1981-05-18 IT IT21786/81A patent/IT1136602B/en active
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- 1981-05-19 YU YU1291/81A patent/YU42012B/en unknown
- 1981-05-19 ES ES502333A patent/ES502333A0/en active Granted
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JPS57500614A (en) | 1982-04-08 |
MX158979A (en) | 1989-04-05 |
ES8203394A1 (en) | 1982-04-01 |
WO1981003333A1 (en) | 1981-11-26 |
PT73055A (en) | 1981-06-01 |
PT73055B (en) | 1982-07-01 |
IT1136602B (en) | 1986-09-03 |
BE888865A (en) | 1981-09-16 |
YU129181A (en) | 1983-06-30 |
CA1206298A (en) | 1986-06-17 |
BR8108609A (en) | 1982-04-06 |
IT8121786A0 (en) | 1981-05-18 |
JPH048442B2 (en) | 1992-02-17 |
EP0051678B1 (en) | 1986-09-03 |
YU42012B (en) | 1988-04-30 |
ES502333A0 (en) | 1982-04-01 |
EP0051678A1 (en) | 1982-05-19 |
GR75231B (en) | 1984-07-13 |
IN151754B (en) | 1983-07-23 |
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